Synthesis of soluble polyarylenes containing alternating 4,4′-(1,1′-binaphthyl) and 4,4′-(3,3′-diphenyl)biphenyl structural units

Summary The synthesis and Ni(0) catalyzed homocoupling polymerization of 4,4-bis[5-(trifluoromethanesulfonyloxy)-2-biphenylyl]-1, 1-binaphthyl (9) are described. This polymerization reaction produces a soluble polyarylene containing alternating 4,4-(1,1-binaphthyl) and 4,4-(3,3-diphenyl)biphenyl structural units.     

4,4′二氨基二苯醚

一、前言 4,4’二氨基二苯醚别名氧撑二苯胺,简称DADPE。日本1992年产量为200吨,主要生产厂家为歌山精细化学工业公司,产品由日本三井东压公司负责销售,日本年需求量为300吨,其中100吨从美国杜邦化学公司进口,供应日本东丽公司。美国杜邦公司1992年产量为1000吨。DADPE主要是制备聚酰亚胺树脂及共塑制品。我国目前生产有天津     

Pervaporation of water/acetic acid through polyimide membranes from 3,3′, 4,4′-benzophenone tetracarboxylic dianhydride and 4,4′-oxydianiline

Summary Pervaporation performance of polyimide (PI) membrane from 3,3, 4,4-benzophenone tetracarboxylic dianhydride (BTDA) and 4,4-oxydianiline (ODA) was investigated at 80wt% feed acetic acid concentration and at 65°C. Imide contents in PI film were estimated by thermogravimetric analysis (TGA) method. The separation factor of PI membrane increases with the degree of imidization, while the flux was almost constant. The separation factor toward water through PI-94 membrane was about 417 with the flux of 47 g/m². hr measured at 65°C and with 80wt% acetic acid as a feed. PI-94 showed the best pervaporation performance toward the separation of water from acetic acid solution among the PI membranes investigated. The swelling behaviors at various feed concenration were also examined.     

Two-dimensional assembling of 4,4′-bipyridine and 4,4′-azopyridine bridged iron (II) linear coordination polymers via hydrogen bond

Novel two-dimensional polymers, [Fe(L¹)(H₂O)₂(NCX)₂] · L¹ (L¹ = 4,4′-bipyridine (bipy)) (1, 2) and [Fe(L²)(CH₃OH)₂-(NCX)₂] · L² (L² = 4,4′-azopyridine (azpy)) (3) and X = S (1,3),Se (2), have been synthesized and characterized by X-ray crystallography. The structures reveal the formation of trans-L-bridged [Fe(NCX)₂(Y)₂] where Y = H₂O, CH₃OH linear chains assembled into two-dimensional networks by hydrogen bonds between the uncoordinated ligand L and the coordinated solvent molecules.     

The electrochemical properties of polyaniline derivatives: poly(4,4′-diphenylamine methylenes) and poly(4,4′-diphenylimine methines)

Summary The electrochemical properties of poly(4,4-diphenylamine methylenes) and poly(4,4-diphenylimine methines) were investigated by cyclic voltammetry. A dehydrogenation reaction occured when poly(4,4-diphenylamine methylenes) underwent a electrochemical reaction and transformed to poly(4,4-diphenylimine methines). The fully oxidized poly(4,4-diphenylimine methines) had the electrochemical band gaps of 1.60–1.72 eV, which were found to significantly smaller than those of the fully reduced poly(4,4-diphenylamine methylenes).     

4,4′-二氨基二苯砜

【王严情沉】 日本和歌山厂年生产4,4尸一二氨基二苯矾30~40吨。【简称】4,4‘一nDS 【性状】白色柱状结晶,熔点1油~179℃,在空气中的热稳定性好,从280℃开始慢慢分解。比热1 .98焦耳/克·度〔100℃),微溶于水(0 .08克/100克,50℃),可溶于乙醇、三氯甲烷、乙腊及其它质子惰性极性有机溶剂等,也溶于稀矿酸。 【市销产品规格】 外观:淡黄白色粉末 比重:1.33 熔点:>176℃ 纯度:>99% 水分:<0.15% 灰分:<0.注% t制法】以对一硝基氯苯或氯苯为原料,照下述方法合成: (1)使硫化钠与对一硝基氯苯反应,生成二稍基二苯硫醚,氧化后则生成二硝基二苯枫,…     

Syntheses and properties of aromatic polyamides derived from 4,4′-oxydibenzoic acid and aromatic diamines

A series of aromatic polyamides were synthesized by direct polycondensation of 4,4-oxydibenzoic acid with various aromatic diamines inN-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride, using triphenyl phosphite and pyridine as condensing agents. The resultant polyamides had inherent viscosities of 0.21-1.48 dL/g. Most of the polymers were organo-soluble and could be solution-cast into flexible and strong films. The glass transition temperatures (T_gs) of most polyamides could be determined with the help of differential scanning calorimetry (DSC) traces, which were recorded in the range of 170–275 °C. Thermogravi metric data of these polymers indicated that most of the polyamides showed no significant weight loss before 450 °C in either air or nitrogen atmospheres.     

催化加氢制备4,4′-ODA研究进展

综述了催化加氢制备4,4′-二氨基二苯醚(4,4′-ODA)的研究进展，重点介绍了加氢催化剂、催化工艺和溶剂的选择。负载型镍(Ni)基催化剂、包覆Ni纳米颗粒催化剂和非晶态Ni-B合金催化剂均表现出优异的加氢活性和选择性，有望取代传统的贵金属加氢催化剂。混合溶剂比单一溶剂更理想，可以提高产品的收率和纯度。未来的发展重点是开发催化加氢连续化生产工艺及相应的催化剂，以降低生产成本，提高产品质量。     

4,4′—二氯二苯砜的合成

4,4′-二氯二苯砜(DCDPS)是一种重要的有机合成产品,它是新型工程塑料——聚砜和聚芳醚砜的一种重要中间体,由它衍生的4,4′-二氨二苯砜、4,4′-二乙酰氨二苯砜是重要的医药原料,4,4′-二氨二苯砜同时也是新型聚芳酰胺砜的单体。此外它的其它一系列衍生物,例如4,4′-二羟二苯砜,     

Sulfonated polyimide copolymers based on 4,4′-diaminostilbene-2,2′-disulfonic acid and 3,5,3′,5′-tetramethylbenzidine with enhanced solubility

A new series of six-membered ring sulfonated polyimides with different combinations of two comonomers in the nonsulfonated diamine was prepared by one-step high-temperature polycondensation in m-cresol to improve the solubility of the resulting sulfonated polyimides. They are based on 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4′-diaminostilbene-2,2-disulfonic acid sulfonated diamine, and equimolar mixture of 3,5,3′,5′-tetramethylbenzidine (TMB) and 4,4′-oxydianiline, bis(4-aminophenyl)methane, or bis(4-(aminophenoxy)-4-phenyl)isopropylidene nonsulfonated diamines. The introduction of TMB comonomer in the nonsulfonated diamine resulted in a remarkable improvement in the solubility of the resulting polyimides in comparison with the corresponding single-monomer nonsulfonated diamine polyimides. Flexible, transparent, and tough membranes were prepared by solution casting method from the different polyimides. The membranes were characterized with FTIR and ¹H-NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, water uptake, and ion-exchange capacity measurements. They exhibit high thermal stability and good correlation between the ion-exchange capacity and water uptake values.     

Preparation and thermotropic properties of copoly(4,4′-biphenylene sebacate-co-eicosanedioate)s

Summary A series of thermotropic copoly(4,4-biphenylene sebacate-co-eicosanedioate)s were prepared by melt polycondensation of 4,4-biphenylene diacetate, sebacic acid and eicosanedioic acid. Their thermal transitions and liquid crystalline properties were investigated by DSC and polarized micrrocope. The copolyesters were found to exhibit a smectic phase, but no nematic phase was observed upon cooling. The smectic-isotropic transition temperature decreased as the content of eicosanedioate unit increased, and the corresponding transition heat did not change to a great extent. However, the crystalline-smectic transition temperature showed an eutectic behavior, and the crystalline-smectic transition heat was depressed considerably after copolymerization. The X-ray diffraction data of the copolyesters after thermal treatment were measured and compared with the thermal properties measured by DSC.     

4,4′-二(氯甲基)联苯和4,4′-联苯二甲醛的合成

以联苯(0．2mol)为原料，依次加入聚甲醛(0．55mol)，无水氯化锌(0．12mol)。环己烷(77mol)，在40℃时滴加20ml氯化亚砜，在40℃～50℃反应至终点，得4，4′-二(氯甲基)联苯(收率46％)。将六甲基四胺(4．8mol)溶于90ml乙醇，在40℃时加入4．4′-二(氯甲基)联苯(1．2mol)，在45℃～50℃时反应1．5小时至终点，再用50％乙酸水解．得4，4′-联苯二甲醛(收率67％)。     

4,4′-二苯甲烷二胺与碳酸二甲酯合成4,4′-二苯甲烷二氨基甲酸甲酯

研究了无水乙酸锌〔Zn(CH3COO)2〕催化下4,4′-二苯甲烷二胺(MDA)与碳酸二甲酯(DMC)合成4,4′-二苯甲烷二氨基甲酸甲酯(MDC)的反应。用高效液相色谱/质谱/质谱联用仪对反应体系副产物进行了检测分析。结果表明,MDC生成的适宜工艺条件为:催化剂用量n〔Zn(CH3COO)2〕∶n(MDA)=5∶1,反应物配比n(DMC)∶n(MDA)=20∶1,反应温度180℃,反应时间2 h。在该条件下MDC收率为98%,MDA转化率100%。分析结果表明,主要副产物为单氨基甲酸酯和3种N-甲基化物。在上述基础上,讨论了N-甲基化物可能的生成机制和副产物的形成对MDC生成的影响。     

4,4′-氧化双苯磺酰氯的合成

介绍了用二苯醚为原料,经浓硫酸磺化、再与三氯氧磷反应制备4,4′-氧化双苯磺酰氯的方法。与二苯醚直接同氯磺酸反应的制法相比,产率高、产品纯,并易于工业化。     

4,4′—二硝基二苯醚的合成

本文用Ｎ，Ｎ－二甲基乙酰胺为溶剂，在适量水存在下，对硝基氯苯为原料，合成４，４一二硝基二苯醚的方法。当溶剂与水的比例为２３：１时，产率可达９８．１％。     

联苯-4,4′-二甲酸合成研究

研究联苯-4,4′-二甲酸的合成工艺,以对硝基甲苯为原料,经氧化、还原和重氮化-偶联反应制备联苯-4,4′-二甲酸。重点研究了重氮反应中滴加亚硝酸对反应的影响。以对硝基甲苯计,总收率为66.6%,联苯-4,4′-二甲酸的(HPLC)纯度为98.7%。     

4,4′-联吡啶的合成工艺概述

4,4′-联吡啶(1)是灭生性除草剂百草枯(Paraquat)(2)的主要中间体。1870年Anderson合成了第一个联吡啶类化合物,以后由Weidel和Russo证明该化合物是4,4′-联吡啶。1923年O.R.Smith对该化合物的合成作了较多阐述,并介绍了由吡啶与金属钠     

4,4′-二碘联苯的合成

以联苯和碘为原料,采用直接碘化法合成了4,4′-二碘联苯。重点考察了物料配比、反应介质中水量、催化剂种类、温度对反应的影响。优化的工艺条件为:n(联苯)∶n(碘)∶n(过硫酸铵)=1∶1.1∶1.1,反应介质为冰乙酸和水,催化剂为浓硫酸,反应温度为85℃,产品收率为86.21%。     

PREPARATION OF 4,4′-DIAMINOSTILBENE-2,2′-DISULFONIC ACID BY CATALYTIC HYDROGENATION

INTRODUCTION4 ,4′ Diaminostilbene 2 ,2′ disulfonicacid (DAS)isanimportantintermediatewhichiswidelyusedinsynthesisoffluorescentwhiteningagents ,directdyesandreactivedyes[1,2 ] .Sofar ,theconventionalprocedureusingFeascatalystfortheproductionofDASinChinai…     

4,4′-二苯醚二甲酸合成工艺研究

研究了以4,4′-二甲基二苯醚为原料,空气液相催化反应合成4,4′-二苯醚二甲酸。讨论了不同催化剂、催化剂用量、不同溶剂对反应收率的影响,优选出较佳的反应条件。收率达90%,产品纯度达99%。该合成方法收率高、操作简便、母液可反复套用、可减少环境污染,具有工业化生产价值。